Thermoplastic resinous reaction product of a diglycidyl ether and an amino compound



United States Patent "I e 3,317,411

Patented May 2, 1967 3,317,471 orthoaminophenol, dimethylurea, piperazine, and C- THERMOPLASTIC RESINOUS REACTION PROD- methylpiperazines and the like, may be employed.

UCT OF A DIGLYCIDYL ETHER AND AN The following examples illustrate the present invention AMINO COMPOUND but are not to be construed as limiting:

Wilbur E..Johnson, Lake Jackson, Tex., and Walter A.

Henson, Midland, Mich., assignors to The Pow Chemi- Example 1 cal Company Mldland Mlch" a corpot'atlon of Dela" 40.5 gm. (representing 0.24 equivalents) of diglycidyl ware ether of Bisphenol A and 7.6 gm. of monoethanolamine N0 Drawmg' Egg- 3 5 23 798854 (representing 0.25 equivalents) were combined in a flask and stirred with a slight warming until reaction began. When the reaction had proceeded until the temperature in the flask was about 200 C. and the contents had become quite fluid, the contents were poured onto a fiat sheet of aluminum foil and allowed to cool to room temperature. The cooled product was a clear, friable solid, having a very slight yellow color. This solid product was ground to granules and found to be easily flowmolded in a platen press at 175 C. Such a molded sample was re-ground to granules and was readily remolded under the same conditions. It readily lent itself to the preparation of fibers and films.

The present invention relates to thermoplastic resinous 10 compositions of matter and more particularly to a new class of linear thermoplastic resinous compositions which are capable of being molded, extruded or drawn into useful shapes such as sheets, films or fibers and which new compositions are capable of reacting with organic polyisocyanates, monocarboxylic acids and dicarboxylic acids to form polyurethanes, polyesters, alkyd-type compositions, and the like.

It has now been found that a linear thermoplastic resinous composition can be prepared by reacting in substantially stoichiometric proportions a diglycidyl ether of a polyhydroxy organic compound and an amine com- Example 2 pound having only two amine hydrogen atoms. The re- 41.7 grams (representing 0.245 equivalents) of diaction is carried out at temperatures of from about 20 glyci'dyl th f Bi h l A d 11,64 grams f ili to about 250 C. Good results are obtained when the (representing 0.025 equivalents) were combined in a reactants are employed in Substantially equimoleelllar flask and stirred with warming until reaction began. Proportione The reaction is Somewhat exothermic and When the reaction had proceeded until the temperature the temperature conveniently can be controlled by external .i th fl k was about 220 C, d h contents quite cooling and/or controlled addition of the reactants. fluid the contents were poured onto a fiat sheet of The new Composition is the first lineal P Y TeSiIl aluminum foil and allowed to cool to room temperature. known to the industry- The Prier known P y The cooled product was a clear, friable solid having a resins were all cross-linked thermoset resins which could very slight yellow color.

not he Worked after Curing? The advantages of the to granules and found to be easily flow-molded in a platen new linear resins over the older thermosetting resins are press at 175 C, Such a molded sample was re-ground ObViOllS- Thus, for p the new resins c he r to granules and was readily re-molded under the same peatedly molded, extruded or drawn whereas the thermoondition setting resins must be cured in shape and are usually sub- In a similar manner other diglycidyl ethers may be ject to degradation before any softening is apparent. employed to prepare linear thermoplastic resinous com- The dlglyeldyl ethers of dIhYdIOXY Organic mp n positions which are suitable for forming self-supporting employed as starting materials in accordance with the fil nd/ fibe present invention are compounds generally classed by E l 3 the formula xamp e 537.5 grams (.5 mole) of a diglycidyl ether which is a Bisphenol A-epichlorohydrin condensate resin having HC 'CHTCH"(OA) OR) O CHCHCH 8.00% by weight of epoxy content, was reacted with 31.0 wherein A is a radical having the general formula grams q 0f ethaholamihe in the Presence of 2 568 grams of diethylene glycol ditert-butyl ether as the solvent. After heating for 2 hours at 110 C., the soluwherein R represents a divalent organic radical of a tion was devolatilized usingagood vacuum with controlled polyhydric phenol or alcohol, and n is an integer from 0 heat at 200 C., to obtain a light yellow resinous product to 20, thus one can employ substantially any diglycidyl which could be molded or drawn-out into flexible fibers. ether of a polyhydroxy compound as, for example, the We claim:

diglycidyl ether of p,p'-methylene bisphenol, p,p'-ethyl- 1. A linear, thermoplastic resin consisting essentially of em bisphenol, p,p'-trimethylene bisphenol, p,p-isopropylthe product formed by the reaction of substantially equiidene bisphenol, p,p' tetramethylene bisphenol, p,p'- molecular proportions of a diglycidyl ether of a dihydroxy hydroquinone, resoncinol, catechol, and the lowerpolyorganic compound having the formula mers of these diglycidyl ethers such as the dimers, tri-mers and the like, the novolaks, their halogenated and hywherein n represents an integer from 0 to 20 and a comdrogenated derivatives, ethylene glycol, 1,3-propylene pound having only two amine hydrogen atoms selected glycol, 1,2-propylene glycol, polyalkylene glycols, glycerfrom the group consisting of alkanolamines and aniline, ol, the epoxy resins such as Dow DER, 331, 332, 66-1, 5 said reaction being eifected by mixing said reactants and 664, 667, The Epons of Shell Chemical and the like. heating the resulting mixture at a temperature of about The active-hydrogen compounds which are operative 20 to 250 C. until the reaction is substantially complete. in the present invention are the basic nitrogenous com- 2. A linear, thermoplastic resin consisting essentially of pounds which have two amino hydrogens per molecule. the product formed by the reaction of substantially equi- Thus, ethanolamine, propanolamine, methylamine, ethyl- 70 molar proportions of a diglycidyl ether of a polyhydroxy amine, propylamine, butylamine, aniline, furfurylamine, organic compound having the formula This solid product was ground wherein n represents an integer from 0 to 20 and a compound having only 2 amine hydrogens selected from the group consisting of alkanolamines and aniline, said reaction being effected by mixing the reactants and heating in the presence of a non-reactive solvent for the resultant resin, followed by devolatilization of the resin solution.

References Cited by the Examiner UNITED STATES PATENTS 2,136,928 11/1938 Schlack 2602 2,599,974 6/1952 Carpenter et al. 260-47 2,642,412 6/1953 Newey et a1. 26047 2,723,241 11/ 1955 De Groote et al 26047 2,830,038 4/1958 Pattison 26047 2,831,830 4/1958 Schroedar 26047 2,864,775 12/1958 Newey 26047 2,878,234 3/1959 Peterson 26047 2,935,488 5/1960 Phillips et al. 26047 2,989,498 6/1961 Mackenzie et al. 26047 WILLIAM H. SHORT, Primary Examiner.

HAROLD BURSTEIN, Examiner.

PHILIP E. MANGAN, D. A. HOES, T. D. KERWIN,

A. LIEBERMAN, Assistant Examiners. 

1. A LINEAR, THERMOPLSTIC RESIN CONSISTING ESSENTIALLY OF THE PRODUCT FORMED BY THE REACTION OF SUBSTANTIALLY EQUIMOLECULAR PROPORTIONS OF A DIGYLCIDYL ETHER OF A DIHYDROXY ORGANIC COMPOUND HAVING THE FORMULA (OXIRANYL-CH2-O-((1,4-PHENYLENE)-C(-CH3)2(1,4-PHENYLENE)-O-CH2-CH(-OH)-CH2 -O)N-(1,4-PHENYLENE)C(-CH3)2-(1,4-PHENYLENE)-O-CH2-)-OXIRANE WHEREIN N REPRESENTS AN INTEGER FROM 0 TO 20 AND A COMPOUND HAVING ONLY TWO AMINE HYDROGEN ATOMS SELECTED FROM THE GROUP CONSISTING OF ALKANOLAMINES AND ANILINE, SAID REACTION BEING EFFECTED BY MIXING SAID REACTANTS AND HEATING THE RESULTING MIXTURE AT A TEMPERATURE OF ABOUT 20 TO 250*C. UNTIL THE REACTION IS SUBSTNATIALLY COMPLETE. 